Water soluble azodyestuffs



l atented Oct. 24, 193-; I I

" iiUNITED STATES PATENT OFFICE 3 3% WATER SOLUBLE AZODYESTUFFS Rudolf Bauer, Cologne-Deutz, Germany, assignor to General AnilineWorks, 'Inc., New York,

N. Y., a corporation of Delaware No1Drawing. Application February 1,' 1932, Serial No. 590,314, and in Germany February 12 Claims. (c1. 2 -7s) The present invention relates to a process-of preparing water soluble azodyestuffs' and to the products obtained thereby, more particularly it relates to disazodyestufis which, may be represented by the probable general formula:

(R N=NxN=NR +SO I-I,

wherein :1: represents a diphenylor diphe'nylurea dicarboxylic acid radical, one R1" represents the 1 radical of an acetoacetic arylamide and the other R1 represents a pyrazolone radical, the sulfonic,

acid group probablystanding in -the aromatic nucleus or" the acetoacetic arylamide radical,

The new water soluble'azodyestufis otthe above general formula are prepared by starting with an azodyestufi of the general formula:

wherein the figures "a: and R1 mean theflsame as stated above, and sulfonating the same withone of the usualsulfonating agents, such as sulfuric acid monohydrate, sulfuric acid containing su1- furic anhydride, chlorosulfonic acid, andthe like, until .a test portion has becomesoluble in aqueous alkalies. 1

The starting disazodyestuffs can be prepared in the usual manner by tetrazotizing a 4.4'-diaminodiphenyl-3.3- dicarboxylic acid or a 4.4diamino,

diphenylurea-33'-dicarboxylio acid and coupling. in any course of succession with one molecular proportion of an acetoacetic arylamide and on molecular proportion of a pyrazolone.

As coupling components there may be mentioned by way of example acetoacetic anilide, I

acetoacetic-o-chloroanilide, acetoacetic anisidi'de,

acetoacetic-u-naphthylamide, methylphenylpyy' The invention isillustrated by the following examples, without being limited thereto:

Example 1.200-parts by weight of. the disazo dyestufl obtainable, from one molecule of 4,459 diaminodiphenylurea-33-dicarboxylici acid, one

molecule of acetoacetic-o-anisidide and one molecule oi m aminophenylmethylpyrazoloneare 1ntroducedat +5 G. into 2,000 parts by weight oi sulfuric acid monohydrate. When'a test por tion of the dyestuff hasbecome soluble in sodium carbonate, the sulfonation mixture :is poured in its free'state the following probableformula:

is stirred with sodium carbonate solution and dried; In the form of its-alkali metal salts it is a brown powder, which on being dyed on cotton and subjected to after-treatment with copper salts, yields an orange, fast to light and washing.

Example 2.,200 parts by weight of the disazodyestufi obtainable from one molecule of li -diaminodiphenyl-3.3 dicarboxylic acid, one molecule of acetoacetico.-anisidide and one molecule of In-aminophenylmethylpyrazolone are introduced at +5 C. into 2000 parts by weight of sulfuric acid monohydrate. When a test portion of the dyestuff has become soluble in aqueous sodi+ um carbonate, the sulfonation mixture is'poured are in the form I "into'10,000,parts-of ice waterand'the'dyestuif, which separates, is filtered. The 'dye'stufi having I into 10000 parts of ice water, and the dyestuff, until a test portion is soluble in sodium carbonate which separates, is filtered. The dyestuff having solution.

in its free state the following formula:

HOaS- is stirred with sodium carbonate solution and dried. In the form of its alkali metal salts it is a brown powder, which on being dyed on cotton and subjected to after-treatment with copper salts, yields a brown, fast to light and Washing.

I claim: 7

1. The process which comprises causing a sulfonating agent to act on an azodyestuif of the probable general formula:

' l HOOO COOH I 'COOH aryl wherein aryl stands for a radical of the benzene series and R1 stands for a pyrazolone radical, until a test portion is soluble in aqueous alkalies.

i. The process which comprises j causing sulfuric acid monohydrate to act on the dyestufi of the following formula:

(IJOOH CIOOH 5. The process which comprises causing a sulfonating agent to act on an azodyestuff oi the probable general formula 00011 UOOH wherei'n'one R1 represents the radical of an acetoacetic arylaniide and the other; R1 represents a pyrazolone radical, until a test portion is soluble in aqueous alkal'ies.

6. The process which comprises causing sulfuric acid monohydrate to act on the azodyestuff of the following formula:

(I3Hs 01:0 1 00 N 1 H000 coon v N l OCH:

until a test portion is soluble in aqueous alkalies',

wherein :1: represents a diphenylor diphenylurea dicarboxylic acid radical, in which the carboxylic OOH acid groups stand in o-position tothe azo-bridges,

10. The compound of the following probable their alkali metal salts water soluble yellowish to brownish powders, dyeing the cellulosic fibre genformula:

CH: A 00011 00011 J 0 g V CH: H& N=N NH-o 0-NH N=N-CH-I l NH N OCH:

HO; NH]

erally yellow to brown shades which, by the after being in the form of its alkali metal salts a yellowtreatment with copper salts, yield full and clear ish brown powder, dyeing the cellulosic fibre dyeings of good fastness to light and washing. yellow shades which, by after-treatment with 8. The compounds of the probable general copper salts, yield an orange, fast to light and formula: washing. to

COOH COOH wherein one R1 represents the radical of an 11. The compounds of the probable general 109 acetoacetic arylamide and the other R1 represents formula:

I I COOH COOH arylwherein aryl stands for a radical of the benzene series and R1 stands for a pyrazolone radical, the sulfonic acid group probably standing in the aromatic nucleus of the acetoacetic arylamide radical, being in the form of their alkali metal salts water soluble yellowish to brownish powders, dyeing the cellulosic fibre generally yellow to 11 brown shades which, by the after-treatment with a pyrazolone radical, the sulfonic acid group probably standing in the aromatic nucleus of the acetoacetic arylamide radical, being in the form of their alkali metal salts water soluble yellowish to brownish powders, dyeing the cellulosic fibre generally yellow to brown shades which, by the after-treatment with copper salts, yield full and clear dyeings of good fastness to light and washing. 7

9. The compounds of the probable general forpp r sa ts, yi ld fu l and l a dy in s f od mula: fastness to light and washing. (Hie-C O(IJH-N=N NHG d-NHQlhN-R, SOaH coon OOH aryl wherein aryl stands for a radical of the ben- 12. The compound of the following probable 25 zene series and R1 stands for a pyrazolone. radical, formula:

V on; i I

, 0 a on, H(:JN=N N=N-cH-c 130 f coon 00H G i I NH N 0 CHI 1 H.058 NH:

being in the form of its alkali metal salts a brown powder, dyeing the cellulosic fibre brown shades, 111-1? which, by the after-treatment with copper salts, yield a brown fast to light and washing the sulfonic acid group probably standing in the aromatic nucleus of the acetoacetic arylamide radical, being in the form of their alkali metal salts water soluble yellowish to brownish powders, dyeing the cellulosic fibre generally yellow to brown shades which, by the after-treatment with copper salts, yield full and clear dyeings of good fastness to light and washing.

' RUDOLF BAUER. 

